Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807024440/fj2033sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807024440/fj2033Isup2.hkl |
CCDC reference: 651445
Key indicators
- Single-crystal X-ray study
- T = 160 K
- Mean (C-C)= 0.004 Å
- R factor = 0.058
- wR factor = 0.165
- Data-to-parameter ratio = 16.3
checkCIF/PLATON results
No syntax errors found No errors found in this datablock
For related literature, see: Wichmann et al. (1999); El-Bendary et al. (1998); Kirpal (1999); Tsuji & Ishikawa (1994); Mohan et al. (1989); Baraldi et al. (1996); Baraldi et al. (2003); Sanjay et al., (2006).
To the Vilsmeier–Haack complex, prepared from DMF (30 ml) and POCl3 (4.6 g, 0.03 mol) at 273–278 K was added 1-(4-chloro-phenylethanone-(4,6-dimethylpyrimidin-2-yl)hydrazone (2.74 g, 0.01 mol). The reaction mixture was stirred at 333–343 K for 4 h, and monitored by TLC. The contents were cooled, poured into ice cold water and neutralized using sodium carbonate. The product that separated was filtered and recrystallized from ethyl acetate to give yellow crystals (2.1 g, 67%).
H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.95–0.98 Å and Uiso=1.2 or 1.5 times Ueq(C).
Literature surveys shows that large numbers of simple, N–bridged, nitrogen and sulfur containing heterocyclic compounds carrying pyrimidine moiety are found to be associated with diverse biological activities, (Wichmann et al., 1999; El-Bendary et al., 1998; Kirpal, 1999; Tsuji & Ishikawa, 1994). Pyrazoles constitute an important class of heterocycles, which display interesting biological properties such as fungicidal, anti-inflamatory, anti-arthritic, anti-depressant and antiviral activity. Many pyrazolines find industrial use as polymer intermediates (Mohan et al., 1989; Baraldi et al., 1996; Baraldi et al., 2003; Sanjay et al., 2006).
The asymmetric unit of (I), Fig. 1, contains two crystallographically independent molecules, A and B. The pyrazole ring of A makes dihedral angles of 5.8 (1)° and 7.2 (1)° with the pyrimidine ring and the phenyl ring respectively; the corresponding values in molecule B are 7.1 (1)° and 13.4 (1)°. The independent molecules contain intramolecular C32A—H32A···N2A, C32B—H32B···N2B, C36A—H36A···O41A, and C36B—H36B···O41B, hydrogen bonds. Further, the molecules A and B are linked by a number of relatively short C—H···N and C—H···O intermolecular contacts.
For related literature, see: Wichmann et al. (1999); El-Bendary et al. (1998); Kirpal (1999); Tsuji & Ishikawa (1994); Mohan et al. (1989); Baraldi et al. (1996); Baraldi et al. (2003); Sanjay et al., (2006).
Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2003).
Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level. |
C16H13ClN4O | Z = 4 |
Mr = 312.75 | F(000) = 648 |
Triclinic, P1 | Dx = 1.453 Mg m−3 |
Hall symbol: -P 1 | Melting point: 442(1) K |
a = 7.2458 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 13.6704 (4) Å | Cell parameters from 53782 reflections |
c = 14.4757 (3) Å | θ = 2.0–27.5° |
α = 90.718 (2)° | µ = 0.28 mm−1 |
β = 92.618 (2)° | T = 160 K |
γ = 93.623 (1)° | Block, light brown |
V = 1429.33 (6) Å3 | 0.38 × 0.23 × 0.20 mm |
Nonius KappaCCD area-detector diffractometer | 6537 independent reflections |
Radiation source: Nonius FR590 sealed tube generator | 5563 reflections with I > 2σ(I) |
Horizontally mounted graphite crystal monochromator | Rint = 0.060 |
Detector resolution: 9 pixels mm-1 | θmax = 27.5°, θmin = 2.0° |
φ and ω scans with κ offsets | h = −9→9 |
Absorption correction: multi-scan (Blessing, 1995) | k = −17→17 |
Tmin = 0.830, Tmax = 0.948 | l = −18→18 |
34357 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 1.17 | w = 1/[σ2(Fo2) + (0.0681P)2 + 1.7016P] where P = (Fo2 + 2Fc2)/3 |
6537 reflections | (Δ/σ)max < 0.001 |
401 parameters | Δρmax = 0.42 e Å−3 |
0 restraints | Δρmin = −0.46 e Å−3 |
C16H13ClN4O | γ = 93.623 (1)° |
Mr = 312.75 | V = 1429.33 (6) Å3 |
Triclinic, P1 | Z = 4 |
a = 7.2458 (2) Å | Mo Kα radiation |
b = 13.6704 (4) Å | µ = 0.28 mm−1 |
c = 14.4757 (3) Å | T = 160 K |
α = 90.718 (2)° | 0.38 × 0.23 × 0.20 mm |
β = 92.618 (2)° |
Nonius KappaCCD area-detector diffractometer | 6537 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 5563 reflections with I > 2σ(I) |
Tmin = 0.830, Tmax = 0.948 | Rint = 0.060 |
34357 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 1.17 | Δρmax = 0.42 e Å−3 |
6537 reflections | Δρmin = −0.46 e Å−3 |
401 parameters |
Experimental. Solvent used: Ethyl acetate Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 1.077 (2) Frames collected: 374 Seconds exposure per frame: 72 Degrees rotation per frame: 1.8 Crystal-Detector distance (mm): 30.0 |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.51295 (10) | 0.68301 (5) | 0.01191 (4) | 0.0365 (2) | |
O41A | 0.5611 (3) | 0.74111 (14) | 0.48792 (13) | 0.0342 (6) | |
N1A | 0.7911 (3) | 0.43476 (14) | 0.48997 (13) | 0.0218 (5) | |
N2A | 0.7564 (3) | 0.45038 (14) | 0.39789 (13) | 0.0221 (5) | |
N12A | 0.9017 (3) | 0.28056 (15) | 0.46061 (14) | 0.0241 (6) | |
N16A | 0.8668 (3) | 0.34137 (15) | 0.61465 (14) | 0.0224 (6) | |
C3A | 0.6944 (3) | 0.54000 (16) | 0.39297 (16) | 0.0206 (6) | |
C4A | 0.6906 (3) | 0.58290 (17) | 0.48430 (16) | 0.0219 (6) | |
C5A | 0.7543 (3) | 0.51247 (17) | 0.54265 (17) | 0.0229 (7) | |
C11A | 0.8575 (3) | 0.34531 (17) | 0.52289 (16) | 0.0216 (6) | |
C13A | 0.9668 (3) | 0.19776 (17) | 0.49692 (17) | 0.0252 (7) | |
C14A | 0.9818 (3) | 0.18455 (18) | 0.59144 (18) | 0.0267 (7) | |
C15A | 0.9311 (3) | 0.25858 (18) | 0.64966 (16) | 0.0236 (6) | |
C31A | 0.6484 (3) | 0.57771 (17) | 0.30050 (16) | 0.0213 (6) | |
C32A | 0.6891 (3) | 0.52279 (17) | 0.22255 (16) | 0.0237 (7) | |
C33A | 0.6465 (4) | 0.55425 (18) | 0.13403 (17) | 0.0271 (7) | |
C34A | 0.5645 (3) | 0.64273 (18) | 0.12273 (17) | 0.0256 (7) | |
C35A | 0.5241 (3) | 0.69938 (18) | 0.19835 (18) | 0.0259 (7) | |
C36A | 0.5643 (3) | 0.66604 (18) | 0.28682 (17) | 0.0258 (7) | |
C41A | 0.6371 (4) | 0.67460 (18) | 0.52475 (17) | 0.0267 (7) | |
C44A | 1.0221 (4) | 0.1229 (2) | 0.42840 (19) | 0.0342 (8) | |
C46A | 0.9439 (4) | 0.25196 (19) | 0.75273 (17) | 0.0278 (7) | |
Cl2 | −0.16204 (10) | 0.51727 (5) | −0.18594 (5) | 0.0392 (2) | |
O41B | 0.0848 (3) | 1.00278 (14) | −0.23689 (13) | 0.0395 (7) | |
N1B | 0.2953 (3) | 1.00178 (14) | 0.06769 (13) | 0.0213 (6) | |
N2B | 0.2305 (3) | 0.90661 (14) | 0.05160 (14) | 0.0221 (6) | |
N12B | 0.3945 (3) | 0.96995 (15) | 0.22009 (14) | 0.0243 (6) | |
N16B | 0.4076 (3) | 1.13192 (15) | 0.15907 (14) | 0.0237 (6) | |
C3B | 0.1713 (3) | 0.90258 (17) | −0.03703 (15) | 0.0194 (6) | |
C4B | 0.2013 (3) | 0.99737 (17) | −0.07844 (16) | 0.0217 (6) | |
C5B | 0.2803 (3) | 1.05697 (17) | −0.00814 (16) | 0.0226 (6) | |
C11B | 0.3705 (3) | 1.03589 (17) | 0.15578 (16) | 0.0216 (6) | |
C13B | 0.4647 (4) | 1.00728 (19) | 0.30196 (17) | 0.0266 (7) | |
C14B | 0.5048 (3) | 1.10726 (19) | 0.31526 (17) | 0.0269 (7) | |
C15B | 0.4774 (3) | 1.16840 (18) | 0.24049 (17) | 0.0243 (7) | |
C31B | 0.0901 (3) | 0.80849 (17) | −0.07541 (16) | 0.0214 (6) | |
C32B | 0.0442 (4) | 0.73270 (19) | −0.01571 (18) | 0.0310 (8) | |
C33B | −0.0313 (4) | 0.6433 (2) | −0.0493 (2) | 0.0349 (8) | |
C34B | −0.0604 (3) | 0.62868 (18) | −0.14341 (19) | 0.0269 (7) | |
C35B | −0.0130 (4) | 0.7013 (2) | −0.20448 (18) | 0.0321 (8) | |
C36B | 0.0617 (4) | 0.79150 (19) | −0.17014 (18) | 0.0294 (7) | |
C41B | 0.1626 (4) | 1.04061 (19) | −0.16822 (17) | 0.0285 (7) | |
C44B | 0.5025 (5) | 0.9345 (2) | 0.37569 (19) | 0.0394 (9) | |
C46B | 0.5244 (4) | 1.27659 (19) | 0.24509 (19) | 0.0323 (8) | |
H5A | 0.76945 | 0.51769 | 0.60810 | 0.0274* | |
H14A | 1.02609 | 0.12587 | 0.61604 | 0.0320* | |
H32A | 0.74699 | 0.46284 | 0.23056 | 0.0285* | |
H33A | 0.67301 | 0.51584 | 0.08170 | 0.0325* | |
H35A | 0.46969 | 0.76023 | 0.18981 | 0.0311* | |
H36A | 0.53419 | 0.70385 | 0.33889 | 0.0309* | |
H41A | 0.66616 | 0.68331 | 0.58911 | 0.0320* | |
H44A | 0.91088 | 0.08764 | 0.40056 | 0.0513* | |
H44B | 1.09989 | 0.07644 | 0.45998 | 0.0513* | |
H44C | 1.09147 | 0.15590 | 0.37990 | 0.0513* | |
H46A | 1.07426 | 0.25825 | 0.77451 | 0.0417* | |
H46B | 0.88815 | 0.18848 | 0.77132 | 0.0417* | |
H46C | 0.87780 | 0.30481 | 0.77992 | 0.0417* | |
H4A | 0.38606 | 0.89951 | 0.39133 | 0.0591* | |
H4B | 0.55884 | 0.96872 | 0.43085 | 0.0591* | |
H4C | 0.58734 | 0.88742 | 0.35318 | 0.0591* | |
H5B | 0.31737 | 1.12461 | −0.01242 | 0.0271* | |
H6A | 0.59384 | 1.29624 | 0.19111 | 0.0484* | |
H6B | 0.59991 | 1.29309 | 0.30168 | 0.0484* | |
H6C | 0.41009 | 1.31127 | 0.24549 | 0.0484* | |
H14B | 0.54977 | 1.13317 | 0.37380 | 0.0323* | |
H32B | 0.06511 | 0.74263 | 0.04909 | 0.0372* | |
H33B | −0.06302 | 0.59224 | −0.00784 | 0.0418* | |
H35B | −0.03094 | 0.68996 | −0.26925 | 0.0385* | |
H36B | 0.09374 | 0.84217 | −0.21193 | 0.0353* | |
H41B | 0.20395 | 1.10753 | −0.17374 | 0.0342* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0482 (4) | 0.0357 (3) | 0.0253 (3) | 0.0061 (3) | −0.0074 (3) | 0.0069 (3) |
O41A | 0.0463 (12) | 0.0249 (9) | 0.0321 (10) | 0.0079 (8) | 0.0013 (8) | −0.0020 (8) |
N1A | 0.0259 (10) | 0.0197 (9) | 0.0192 (9) | −0.0006 (8) | −0.0014 (8) | 0.0011 (7) |
N2A | 0.0263 (10) | 0.0207 (9) | 0.0191 (9) | 0.0013 (8) | −0.0015 (8) | 0.0032 (7) |
N12A | 0.0282 (10) | 0.0204 (10) | 0.0232 (10) | −0.0007 (8) | −0.0019 (8) | 0.0006 (8) |
N16A | 0.0226 (10) | 0.0228 (10) | 0.0215 (10) | −0.0001 (8) | −0.0008 (8) | 0.0023 (8) |
C3A | 0.0206 (11) | 0.0184 (10) | 0.0223 (11) | −0.0019 (8) | 0.0006 (9) | −0.0001 (8) |
C4A | 0.0220 (11) | 0.0213 (11) | 0.0220 (11) | −0.0008 (9) | 0.0013 (9) | 0.0005 (9) |
C5A | 0.0248 (12) | 0.0218 (11) | 0.0216 (11) | −0.0013 (9) | 0.0005 (9) | −0.0007 (9) |
C11A | 0.0205 (11) | 0.0193 (10) | 0.0244 (11) | −0.0013 (8) | −0.0021 (9) | 0.0024 (9) |
C13A | 0.0275 (12) | 0.0208 (11) | 0.0267 (12) | −0.0005 (9) | −0.0005 (9) | −0.0002 (9) |
C14A | 0.0285 (12) | 0.0231 (12) | 0.0284 (12) | 0.0037 (10) | −0.0023 (10) | 0.0042 (9) |
C15A | 0.0233 (11) | 0.0245 (11) | 0.0224 (11) | −0.0020 (9) | −0.0008 (9) | 0.0037 (9) |
C31A | 0.0210 (11) | 0.0189 (10) | 0.0234 (11) | −0.0020 (8) | 0.0001 (9) | 0.0013 (9) |
C32A | 0.0293 (12) | 0.0184 (11) | 0.0236 (12) | 0.0019 (9) | 0.0012 (9) | 0.0016 (9) |
C33A | 0.0345 (13) | 0.0235 (12) | 0.0233 (12) | 0.0001 (10) | 0.0039 (10) | 0.0012 (9) |
C34A | 0.0274 (12) | 0.0262 (12) | 0.0227 (11) | −0.0003 (10) | −0.0020 (9) | 0.0045 (9) |
C35A | 0.0253 (12) | 0.0231 (11) | 0.0296 (12) | 0.0040 (9) | 0.0004 (10) | 0.0038 (9) |
C36A | 0.0284 (12) | 0.0236 (12) | 0.0259 (12) | 0.0049 (9) | 0.0031 (10) | 0.0005 (9) |
C41A | 0.0317 (13) | 0.0250 (12) | 0.0232 (12) | 0.0001 (10) | 0.0029 (10) | −0.0022 (9) |
C44A | 0.0467 (16) | 0.0254 (13) | 0.0307 (14) | 0.0073 (11) | −0.0014 (12) | −0.0035 (10) |
C46A | 0.0334 (13) | 0.0268 (12) | 0.0234 (12) | 0.0036 (10) | −0.0013 (10) | 0.0050 (9) |
Cl2 | 0.0381 (4) | 0.0259 (3) | 0.0514 (4) | −0.0078 (3) | −0.0047 (3) | −0.0083 (3) |
O41B | 0.0637 (14) | 0.0291 (10) | 0.0249 (10) | 0.0072 (9) | −0.0126 (9) | −0.0010 (8) |
N1B | 0.0245 (10) | 0.0181 (9) | 0.0210 (10) | 0.0015 (7) | −0.0024 (8) | −0.0026 (7) |
N2B | 0.0241 (10) | 0.0188 (9) | 0.0228 (10) | −0.0009 (8) | −0.0014 (8) | −0.0032 (7) |
N12B | 0.0276 (10) | 0.0237 (10) | 0.0211 (10) | 0.0007 (8) | −0.0016 (8) | −0.0009 (8) |
N16B | 0.0269 (10) | 0.0208 (10) | 0.0230 (10) | 0.0002 (8) | −0.0015 (8) | −0.0024 (8) |
C3B | 0.0181 (10) | 0.0216 (11) | 0.0188 (10) | 0.0029 (8) | 0.0016 (8) | −0.0024 (8) |
C4B | 0.0231 (11) | 0.0199 (11) | 0.0224 (11) | 0.0047 (9) | 0.0000 (9) | −0.0019 (9) |
C5B | 0.0242 (11) | 0.0194 (11) | 0.0242 (11) | 0.0033 (9) | −0.0020 (9) | 0.0002 (9) |
C11B | 0.0204 (11) | 0.0236 (11) | 0.0207 (11) | 0.0027 (9) | −0.0006 (9) | −0.0037 (9) |
C13B | 0.0296 (13) | 0.0288 (12) | 0.0215 (11) | 0.0030 (10) | 0.0001 (9) | −0.0011 (9) |
C14B | 0.0287 (12) | 0.0283 (12) | 0.0232 (12) | 0.0023 (10) | −0.0039 (9) | −0.0049 (9) |
C15B | 0.0236 (11) | 0.0232 (12) | 0.0258 (12) | 0.0010 (9) | −0.0004 (9) | −0.0058 (9) |
C31B | 0.0193 (10) | 0.0218 (11) | 0.0230 (11) | 0.0022 (9) | −0.0003 (9) | −0.0029 (9) |
C32B | 0.0406 (15) | 0.0284 (13) | 0.0230 (12) | −0.0044 (11) | 0.0005 (10) | −0.0012 (10) |
C33B | 0.0429 (16) | 0.0262 (13) | 0.0347 (14) | −0.0068 (11) | 0.0046 (12) | 0.0047 (11) |
C34B | 0.0206 (11) | 0.0224 (11) | 0.0368 (14) | −0.0017 (9) | −0.0010 (10) | −0.0055 (10) |
C35B | 0.0408 (15) | 0.0299 (13) | 0.0240 (12) | −0.0041 (11) | −0.0058 (11) | −0.0039 (10) |
C36B | 0.0389 (14) | 0.0249 (12) | 0.0236 (12) | −0.0027 (10) | −0.0012 (10) | 0.0007 (10) |
C41B | 0.0385 (14) | 0.0219 (12) | 0.0252 (12) | 0.0057 (10) | −0.0028 (10) | 0.0015 (9) |
C44B | 0.0601 (19) | 0.0315 (14) | 0.0253 (13) | −0.0003 (13) | −0.0086 (12) | 0.0035 (11) |
C46B | 0.0404 (15) | 0.0224 (12) | 0.0328 (14) | −0.0013 (10) | −0.0046 (11) | −0.0068 (10) |
Cl1—C34A | 1.735 (3) | C33A—H33A | 0.9500 |
Cl2—C34B | 1.742 (3) | C35A—H35A | 0.9500 |
O41A—C41A | 1.210 (3) | C36A—H36A | 0.9500 |
O41B—C41B | 1.213 (3) | C41A—H41A | 0.9500 |
N1A—N2A | 1.367 (3) | C44A—H44C | 0.9800 |
N1A—C5A | 1.347 (3) | C44A—H44B | 0.9800 |
N1A—C11A | 1.422 (3) | C44A—H44A | 0.9800 |
N2A—C3A | 1.333 (3) | C46A—H46A | 0.9800 |
N12A—C13A | 1.356 (3) | C46A—H46B | 0.9800 |
N12A—C11A | 1.320 (3) | C46A—H46C | 0.9800 |
N16A—C11A | 1.329 (3) | C3B—C4B | 1.443 (3) |
N16A—C15A | 1.347 (3) | C3B—C31B | 1.472 (3) |
N1B—C5B | 1.344 (3) | C4B—C5B | 1.376 (3) |
N1B—C11B | 1.425 (3) | C4B—C41B | 1.457 (3) |
N1B—N2B | 1.368 (3) | C13B—C14B | 1.388 (4) |
N2B—C3B | 1.333 (3) | C13B—C44B | 1.496 (4) |
N12B—C13B | 1.349 (3) | C14B—C15B | 1.391 (4) |
N12B—C11B | 1.317 (3) | C15B—C46B | 1.497 (4) |
N16B—C11B | 1.323 (3) | C31B—C32B | 1.391 (3) |
N16B—C15B | 1.339 (3) | C31B—C36B | 1.392 (3) |
C3A—C31A | 1.472 (3) | C32B—C33B | 1.380 (4) |
C3A—C4A | 1.442 (3) | C33B—C34B | 1.379 (4) |
C4A—C5A | 1.376 (3) | C34B—C35B | 1.375 (4) |
C4A—C41A | 1.459 (3) | C35B—C36B | 1.392 (4) |
C13A—C14A | 1.383 (4) | C5B—H5B | 0.9500 |
C13A—C44A | 1.501 (4) | C14B—H14B | 0.9500 |
C14A—C15A | 1.387 (3) | C32B—H32B | 0.9500 |
C15A—C46A | 1.495 (3) | C33B—H33B | 0.9500 |
C31A—C32A | 1.400 (3) | C35B—H35B | 0.9500 |
C31A—C36A | 1.399 (3) | C36B—H36B | 0.9500 |
C32A—C33A | 1.384 (3) | C41B—H41B | 0.9500 |
C33A—C34A | 1.389 (4) | C44B—H4A | 0.9800 |
C34A—C35A | 1.386 (4) | C44B—H4B | 0.9800 |
C35A—C36A | 1.389 (4) | C44B—H4C | 0.9800 |
C5A—H5A | 0.9500 | C46B—H6A | 0.9800 |
C14A—H14A | 0.9500 | C46B—H6B | 0.9800 |
C32A—H32A | 0.9500 | C46B—H6C | 0.9800 |
Cl1···C32B | 3.512 (3) | C4A···H36A | 2.9200 |
Cl1···C33Bi | 3.531 (3) | C4B···H36B | 2.9000 |
Cl2···C32Aii | 3.567 (2) | C14A···H4Avi | 2.8600 |
Cl1···H6Aiii | 3.0300 | C15A···H4Avi | 3.0900 |
Cl1···H5Biii | 2.8300 | C33A···H33Bi | 3.0300 |
Cl2···H32Aii | 3.1000 | C34B···H6Cv | 3.0400 |
Cl2···H46Civ | 2.9700 | C34B···H32Aii | 2.9800 |
Cl2···H5Aiv | 3.0000 | C35A···H46Aix | 2.9400 |
Cl2···H6Cv | 3.1500 | C35A···H46Cvi | 2.9400 |
O41A···C44B | 3.162 (3) | C35B···H6Cv | 2.9100 |
O41A···C36A | 3.076 (3) | C35B···H32Aii | 3.0800 |
O41A···C11Avi | 3.181 (3) | C35B···H6Aiii | 3.0300 |
O41B···C36B | 3.054 (3) | C36A···H46Aix | 2.9300 |
O41B···C44Aii | 3.279 (3) | C36B···H6Aiii | 2.8600 |
O41A···H36A | 2.2100 | C41A···H36A | 2.8000 |
O41A···H4A | 2.9200 | C41B···H46Bviii | 3.0300 |
O41A···H4C | 2.8200 | C41B···H36B | 2.7900 |
O41A···H14Bvii | 2.8000 | C46A···H41Bxii | 2.9900 |
O41B···H36B | 2.2300 | C46A···H32Bvi | 2.8700 |
O41B···H14Aviii | 2.7600 | C46B···H41Avii | 2.8900 |
O41B···H44Aii | 2.6600 | C46B···H32Axiii | 2.9400 |
N1A···C5Aix | 3.383 (3) | H4A···O41A | 2.9200 |
N1A···C41Avi | 3.354 (4) | H4A···C14Avi | 2.8600 |
N1B···C5Biii | 3.374 (3) | H4A···C15Avi | 3.0900 |
N2A···N12A | 2.756 (3) | H4B···H14B | 2.4100 |
N2B···N12B | 2.768 (3) | H4B···H4Bvii | 2.3800 |
N12A···C41Aix | 3.356 (4) | H4C···H36A | 2.5200 |
N12A···N2A | 2.756 (3) | H4C···O41A | 2.8200 |
N12A···C4Aix | 3.449 (3) | H5A···N16A | 2.5600 |
N12B···N2B | 2.768 (3) | H5A···Cl2xiv | 3.0000 |
N12B···C41Biii | 3.341 (4) | H5A···H41A | 2.4400 |
N2A···H32A | 2.4300 | H5B···Cl1iii | 2.8300 |
N2A···H6Bx | 2.7100 | H5B···N16B | 2.5400 |
N2B···H32B | 2.4700 | H5B···H41B | 2.4400 |
N12B···H46Bvi | 2.8900 | H6A···H32Axiii | 2.5200 |
N16A···H5A | 2.5600 | H6A···C36Biii | 2.8600 |
N16B···H5B | 2.5400 | H6A···Cl1iii | 3.0300 |
C3A···C5Avi | 3.457 (3) | H6A···C35Biii | 3.0300 |
C3B···C4Bv | 3.574 (3) | H6B···H41Avii | 2.5800 |
C3B···C5Bv | 3.443 (3) | H6B···H14B | 2.4500 |
C4A···C11Aix | 3.365 (3) | H6B···N2Axiii | 2.7100 |
C4A···C5Avi | 3.404 (3) | H6C···C34Bv | 3.0400 |
C4A···C4Avi | 3.510 (3) | H6C···C35Bv | 2.9100 |
C4A···N12Aix | 3.449 (3) | H6C···Cl2v | 3.1500 |
C4B···C3Bv | 3.574 (3) | H6C···H41Avii | 2.4800 |
C4B···C11Biii | 3.401 (3) | H14A···H44B | 2.4400 |
C5A···C11Aix | 3.492 (3) | H14A···O41Bxii | 2.7600 |
C5A···C3Avi | 3.457 (3) | H14B···H6B | 2.4500 |
C5A···C4Avi | 3.404 (3) | H14B···H4B | 2.4100 |
C5A···N1Aix | 3.383 (3) | H14B···O41Avii | 2.8000 |
C5B···N1Biii | 3.374 (3) | H32A···N2A | 2.4300 |
C5B···C3Bv | 3.443 (3) | H32A···C35Bii | 3.0800 |
C5B···C31Bv | 3.594 (3) | H32A···H6Ax | 2.5200 |
C11A···C5Aix | 3.492 (3) | H32A···Cl2ii | 3.1000 |
C11A···C4Aix | 3.365 (3) | H32A···C46Bx | 2.9400 |
C11A···O41Avi | 3.181 (3) | H32A···C34Bii | 2.9800 |
C11B···C4Biii | 3.401 (3) | H32B···C46Avi | 2.8700 |
C13A···C41Aix | 3.293 (4) | H32B···H46Cvi | 2.5900 |
C13B···C41Biii | 3.484 (4) | H32B···N2B | 2.4700 |
C15B···C36Biii | 3.547 (4) | H33A···H33Bi | 2.5400 |
C31B···C5Bv | 3.594 (3) | H33B···H33Axi | 2.5400 |
C32A···C46Bx | 3.523 (3) | H33B···C33Axi | 3.0300 |
C32A···Cl2ii | 3.567 (2) | H36A···C4A | 2.9200 |
C32B···Cl1 | 3.512 (3) | H36A···O41A | 2.2100 |
C33B···Cl1xi | 3.531 (3) | H36A···H4C | 2.5200 |
C35A···C46Avi | 3.597 (4) | H36A···C41A | 2.8000 |
C36A···C41A | 3.460 (3) | H36B···C4B | 2.9000 |
C36A···O41A | 3.076 (3) | H36B···C41B | 2.7900 |
C36B···C41B | 3.437 (4) | H36B···O41B | 2.2300 |
C36B···O41B | 3.054 (3) | H41A···H5A | 2.4400 |
C36B···C46Biii | 3.415 (4) | H41A···H6Cvii | 2.4800 |
C36B···C15Biii | 3.547 (4) | H41A···H6Bvii | 2.5800 |
C41A···C13Aix | 3.293 (4) | H41A···C46Bvii | 2.8900 |
C41A···N12Aix | 3.356 (4) | H41B···H46Aviii | 2.4300 |
C41A···C36A | 3.460 (3) | H41B···H5B | 2.4400 |
C41A···N1Avi | 3.354 (4) | H41B···C46Aviii | 2.9900 |
C41B···N12Biii | 3.341 (4) | H44A···O41Bii | 2.6600 |
C41B···C46Aviii | 3.559 (4) | H44B···H14A | 2.4400 |
C41B···C13Biii | 3.484 (4) | H46A···C36Aix | 2.9300 |
C41B···C36B | 3.437 (4) | H46A···H41Bxii | 2.4300 |
C44A···O41Bii | 3.279 (3) | H46A···C35Aix | 2.9400 |
C44B···O41A | 3.162 (3) | H46B···N12Bvi | 2.8900 |
C46A···C35Avi | 3.597 (4) | H46B···C41Bxii | 3.0300 |
C46A···C41Bxii | 3.559 (4) | H46C···H32Bvi | 2.5900 |
C46B···C32Axiii | 3.523 (3) | H46C···Cl2xiv | 2.9700 |
C46B···C36Biii | 3.415 (4) | H46C···C35Avi | 2.9400 |
N2A—N1A—C5A | 112.13 (19) | H46B—C46A—H46C | 109.00 |
N2A—N1A—C11A | 122.00 (19) | C15A—C46A—H46A | 109.00 |
C5A—N1A—C11A | 125.9 (2) | C15A—C46A—H46B | 109.00 |
N1A—N2A—C3A | 105.52 (18) | C15A—C46A—H46C | 109.00 |
C11A—N12A—C13A | 114.2 (2) | H46A—C46A—H46B | 109.00 |
C11A—N16A—C15A | 115.2 (2) | H46A—C46A—H46C | 109.00 |
C5B—N1B—C11B | 125.1 (2) | N2B—C3B—C4B | 110.1 (2) |
N2B—N1B—C5B | 112.43 (19) | N2B—C3B—C31B | 118.4 (2) |
N2B—N1B—C11B | 122.43 (19) | C4B—C3B—C31B | 131.5 (2) |
N1B—N2B—C3B | 105.31 (18) | C3B—C4B—C5B | 104.8 (2) |
C11B—N12B—C13B | 114.3 (2) | C3B—C4B—C41B | 136.7 (2) |
C11B—N16B—C15B | 115.4 (2) | C5B—C4B—C41B | 118.5 (2) |
N2A—C3A—C4A | 110.2 (2) | N1B—C5B—C4B | 107.3 (2) |
N2A—C3A—C31A | 117.6 (2) | N1B—C11B—N12B | 117.4 (2) |
C4A—C3A—C31A | 132.2 (2) | N1B—C11B—N16B | 112.7 (2) |
C3A—C4A—C5A | 104.7 (2) | N12B—C11B—N16B | 129.9 (2) |
C3A—C4A—C41A | 136.9 (2) | N12B—C13B—C14B | 121.5 (2) |
C5A—C4A—C41A | 118.4 (2) | N12B—C13B—C44B | 116.1 (2) |
N1A—C5A—C4A | 107.5 (2) | C14B—C13B—C44B | 122.4 (2) |
N1A—C11A—N12A | 117.4 (2) | C13B—C14B—C15B | 118.2 (2) |
N12A—C11A—N16A | 130.0 (2) | N16B—C15B—C14B | 120.7 (2) |
N1A—C11A—N16A | 112.7 (2) | N16B—C15B—C46B | 116.3 (2) |
N12A—C13A—C14A | 121.4 (2) | C14B—C15B—C46B | 123.0 (2) |
C14A—C13A—C44A | 122.7 (2) | C3B—C31B—C32B | 119.4 (2) |
N12A—C13A—C44A | 115.9 (2) | C3B—C31B—C36B | 122.2 (2) |
C13A—C14A—C15A | 118.8 (2) | C32B—C31B—C36B | 118.4 (2) |
N16A—C15A—C46A | 116.5 (2) | C31B—C32B—C33B | 120.9 (2) |
N16A—C15A—C14A | 120.6 (2) | C32B—C33B—C34B | 119.5 (2) |
C14A—C15A—C46A | 122.9 (2) | Cl2—C34B—C33B | 119.7 (2) |
C3A—C31A—C36A | 122.9 (2) | Cl2—C34B—C35B | 119.3 (2) |
C3A—C31A—C32A | 118.9 (2) | C33B—C34B—C35B | 121.1 (2) |
C32A—C31A—C36A | 118.3 (2) | C34B—C35B—C36B | 119.1 (2) |
C31A—C32A—C33A | 121.2 (2) | C31B—C36B—C35B | 120.9 (2) |
C32A—C33A—C34A | 119.1 (2) | O41B—C41B—C4B | 128.8 (2) |
Cl1—C34A—C33A | 119.28 (19) | N1B—C5B—H5B | 126.00 |
Cl1—C34A—C35A | 119.58 (19) | C4B—C5B—H5B | 126.00 |
C33A—C34A—C35A | 121.1 (2) | C13B—C14B—H14B | 121.00 |
C34A—C35A—C36A | 119.1 (2) | C15B—C14B—H14B | 121.00 |
C31A—C36A—C35A | 121.1 (2) | C31B—C32B—H32B | 120.00 |
O41A—C41A—C4A | 129.2 (2) | C33B—C32B—H32B | 120.00 |
N1A—C5A—H5A | 126.00 | C32B—C33B—H33B | 120.00 |
C4A—C5A—H5A | 126.00 | C34B—C33B—H33B | 120.00 |
C15A—C14A—H14A | 121.00 | C34B—C35B—H35B | 120.00 |
C13A—C14A—H14A | 121.00 | C36B—C35B—H35B | 120.00 |
C31A—C32A—H32A | 119.00 | C31B—C36B—H36B | 120.00 |
C33A—C32A—H32A | 119.00 | C35B—C36B—H36B | 120.00 |
C32A—C33A—H33A | 120.00 | O41B—C41B—H41B | 116.00 |
C34A—C33A—H33A | 120.00 | C4B—C41B—H41B | 116.00 |
C36A—C35A—H35A | 120.00 | C13B—C44B—H4A | 109.00 |
C34A—C35A—H35A | 120.00 | C13B—C44B—H4B | 110.00 |
C31A—C36A—H36A | 119.00 | C13B—C44B—H4C | 109.00 |
C35A—C36A—H36A | 119.00 | H4A—C44B—H4B | 109.00 |
O41A—C41A—H41A | 115.00 | H4A—C44B—H4C | 109.00 |
C4A—C41A—H41A | 115.00 | H4B—C44B—H4C | 109.00 |
H44A—C44A—H44B | 110.00 | C15B—C46B—H6A | 109.00 |
H44A—C44A—H44C | 109.00 | C15B—C46B—H6B | 109.00 |
C13A—C44A—H44A | 109.00 | C15B—C46B—H6C | 109.00 |
C13A—C44A—H44B | 109.00 | H6A—C46B—H6B | 110.00 |
C13A—C44A—H44C | 109.00 | H6A—C46B—H6C | 109.00 |
H44B—C44A—H44C | 110.00 | H6B—C46B—H6C | 109.00 |
C5A—N1A—N2A—C3A | −0.6 (3) | C41A—C4A—C5A—N1A | 178.9 (2) |
C11A—N1A—N2A—C3A | 179.1 (2) | C3A—C4A—C5A—N1A | −0.4 (2) |
N2A—N1A—C5A—C4A | 0.6 (3) | C5A—C4A—C41A—O41A | −171.7 (3) |
C11A—N1A—C5A—C4A | −179.1 (2) | C3A—C4A—C41A—O41A | 7.2 (5) |
N2A—N1A—C11A—N12A | 6.3 (3) | N12A—C13A—C14A—C15A | −0.9 (3) |
N2A—N1A—C11A—N16A | −174.4 (2) | C44A—C13A—C14A—C15A | 178.6 (2) |
C5A—N1A—C11A—N12A | −174.0 (2) | C13A—C14A—C15A—C46A | −179.4 (2) |
C5A—N1A—C11A—N16A | 5.3 (3) | C13A—C14A—C15A—N16A | 0.6 (3) |
N1A—N2A—C3A—C4A | 0.4 (3) | C3A—C31A—C32A—C33A | 179.1 (2) |
N1A—N2A—C3A—C31A | 178.90 (19) | C36A—C31A—C32A—C33A | −0.4 (3) |
C13A—N12A—C11A—N1A | 179.0 (2) | C3A—C31A—C36A—C35A | 179.6 (2) |
C13A—N12A—C11A—N16A | −0.2 (4) | C32A—C31A—C36A—C35A | −0.8 (3) |
C11A—N12A—C13A—C14A | 0.6 (3) | C31A—C32A—C33A—C34A | 1.0 (4) |
C11A—N12A—C13A—C44A | −178.9 (2) | C32A—C33A—C34A—C35A | −0.3 (4) |
C15A—N16A—C11A—N1A | −179.2 (2) | C32A—C33A—C34A—Cl1 | 179.38 (19) |
C15A—N16A—C11A—N12A | 0.0 (4) | Cl1—C34A—C35A—C36A | 179.39 (17) |
C11A—N16A—C15A—C14A | −0.2 (3) | C33A—C34A—C35A—C36A | −0.9 (3) |
C11A—N16A—C15A—C46A | 179.8 (2) | C34A—C35A—C36A—C31A | 1.5 (3) |
N2B—N1B—C11B—N16B | −173.6 (2) | N2B—C3B—C4B—C5B | −0.5 (3) |
C5B—N1B—C11B—N12B | −172.5 (2) | N2B—C3B—C4B—C41B | −177.3 (3) |
C5B—N1B—C11B—N16B | 6.9 (3) | C31B—C3B—C4B—C5B | 179.4 (2) |
N2B—N1B—C5B—C4B | 0.4 (3) | C31B—C3B—C4B—C41B | 2.5 (5) |
C5B—N1B—N2B—C3B | −0.7 (3) | N2B—C3B—C31B—C32B | 12.4 (3) |
C11B—N1B—N2B—C3B | 179.7 (2) | N2B—C3B—C31B—C36B | −165.9 (2) |
C11B—N1B—C5B—C4B | 180.0 (2) | C4B—C3B—C31B—C32B | −167.4 (2) |
N2B—N1B—C11B—N12B | 7.1 (3) | C4B—C3B—C31B—C36B | 14.3 (4) |
N1B—N2B—C3B—C4B | 0.7 (3) | C3B—C4B—C5B—N1B | 0.1 (2) |
N1B—N2B—C3B—C31B | −179.19 (19) | C41B—C4B—C5B—N1B | 177.6 (2) |
C13B—N12B—C11B—N1B | −179.5 (2) | C3B—C4B—C41B—O41B | 1.2 (5) |
C13B—N12B—C11B—N16B | 1.3 (4) | C5B—C4B—C41B—O41B | −175.4 (3) |
C11B—N12B—C13B—C44B | −177.3 (2) | N12B—C13B—C14B—C15B | −2.5 (4) |
C11B—N12B—C13B—C14B | 0.7 (4) | C44B—C13B—C14B—C15B | 175.3 (3) |
C15B—N16B—C11B—N12B | −1.3 (4) | C13B—C14B—C15B—N16B | 2.5 (3) |
C15B—N16B—C11B—N1B | 179.5 (2) | C13B—C14B—C15B—C46B | −176.9 (2) |
C11B—N16B—C15B—C14B | −0.8 (3) | C3B—C31B—C32B—C33B | −179.7 (2) |
C11B—N16B—C15B—C46B | 178.7 (2) | C36B—C31B—C32B—C33B | −1.3 (4) |
C31A—C3A—C4A—C5A | −178.3 (2) | C3B—C31B—C36B—C35B | 179.1 (2) |
N2A—C3A—C4A—C5A | 0.0 (3) | C32B—C31B—C36B—C35B | 0.8 (4) |
N2A—C3A—C4A—C41A | −179.0 (3) | C31B—C32B—C33B—C34B | 0.5 (4) |
N2A—C3A—C31A—C36A | 173.2 (2) | C32B—C33B—C34B—Cl2 | −178.1 (2) |
C4A—C3A—C31A—C32A | 171.7 (2) | C32B—C33B—C34B—C35B | 0.9 (4) |
C4A—C3A—C31A—C36A | −8.7 (4) | Cl2—C34B—C35B—C36B | 177.6 (2) |
N2A—C3A—C31A—C32A | −6.4 (3) | C33B—C34B—C35B—C36B | −1.4 (4) |
C31A—C3A—C4A—C41A | 2.8 (5) | C34B—C35B—C36B—C31B | 0.5 (4) |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z; (iii) −x+1, −y+2, −z; (iv) x−1, y, z−1; (v) −x, −y+2, −z; (vi) −x+1, −y+1, −z+1; (vii) −x+1, −y+2, −z+1; (viii) x−1, y+1, z−1; (ix) −x+2, −y+1, −z+1; (x) x, y−1, z; (xi) x−1, y, z; (xii) x+1, y−1, z+1; (xiii) x, y+1, z; (xiv) x+1, y, z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C32A—H32A···N2A | 0.9500 | 2.4300 | 2.770 (3) | 101.00 |
C32B—H32B···N2B | 0.9500 | 2.4700 | 2.800 (3) | 100.00 |
C36A—H36A···O41A | 0.9500 | 2.2100 | 3.076 (3) | 152.00 |
C36B—H36B···O41B | 0.9500 | 2.2300 | 3.054 (3) | 144.00 |
Experimental details
Crystal data | |
Chemical formula | C16H13ClN4O |
Mr | 312.75 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 160 |
a, b, c (Å) | 7.2458 (2), 13.6704 (4), 14.4757 (3) |
α, β, γ (°) | 90.718 (2), 92.618 (2), 93.623 (1) |
V (Å3) | 1429.33 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.28 |
Crystal size (mm) | 0.38 × 0.23 × 0.20 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.830, 0.948 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 34357, 6537, 5563 |
Rint | 0.060 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.165, 1.17 |
No. of reflections | 6537 |
No. of parameters | 401 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.42, −0.46 |
Computer programs: COLLECT (Nonius, 2000), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN and SCALEPACK (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
C32A—H32A···N2A | 0.9500 | 2.4300 | 2.770 (3) | 101.00 |
C32B—H32B···N2B | 0.9500 | 2.4700 | 2.800 (3) | 100.00 |
C36A—H36A···O41A | 0.9500 | 2.2100 | 3.076 (3) | 152.00 |
C36B—H36B···O41B | 0.9500 | 2.2300 | 3.054 (3) | 144.00 |
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Literature surveys shows that large numbers of simple, N–bridged, nitrogen and sulfur containing heterocyclic compounds carrying pyrimidine moiety are found to be associated with diverse biological activities, (Wichmann et al., 1999; El-Bendary et al., 1998; Kirpal, 1999; Tsuji & Ishikawa, 1994). Pyrazoles constitute an important class of heterocycles, which display interesting biological properties such as fungicidal, anti-inflamatory, anti-arthritic, anti-depressant and antiviral activity. Many pyrazolines find industrial use as polymer intermediates (Mohan et al., 1989; Baraldi et al., 1996; Baraldi et al., 2003; Sanjay et al., 2006).
The asymmetric unit of (I), Fig. 1, contains two crystallographically independent molecules, A and B. The pyrazole ring of A makes dihedral angles of 5.8 (1)° and 7.2 (1)° with the pyrimidine ring and the phenyl ring respectively; the corresponding values in molecule B are 7.1 (1)° and 13.4 (1)°. The independent molecules contain intramolecular C32A—H32A···N2A, C32B—H32B···N2B, C36A—H36A···O41A, and C36B—H36B···O41B, hydrogen bonds. Further, the molecules A and B are linked by a number of relatively short C—H···N and C—H···O intermolecular contacts.